Benzothiazole monoazo dyes



United States Patent 3,342,800 BENZOTHIAZOLE MONOAZO DYES Jack L. Towle, East Cleveland, and John A. Zelekand George R. Pellon, Cleveland, Ohio, assignors, by mesne assignments, to Kewanee Oil Company, Bryn Mawr, Pa., a corporation of Delaware No Drawing. Original application June 26, 1962, Ser. No. application Dec. 13, 1963,

205,217. Divided and this Ser. No. 330,233

13 Claims. (Cl. 260-158) The application is a divisional application of Ser. No. 205,217, filed June 26, 1962, now abandoned. I

This invention relates to azo dyes. More particularly the invention relates to azo dyes having good dischargeability. I

It has been discovered that the azo compounds having the general formula:

wherein R represents a member selected from the group consisting of H, an alkyl group, an aryl group, or a carbamylalkyl group and R represents a carbamylalkyl group. R and R represent a lower alkyl group, a methoxy group, a halogen atom, or an H atom; have particular utility as dischargeable dyes.

The azo compounds of the instant invention are prepared by diazotizing a 2 amino 6 methylsulfonylbenzothiazole having the formula and coupling these diazonium compounds with compounds having the following general formula:

(III) R Example I N ethyl-p-cyanoethyl m-toluidine (75.3 grams) was slowly added with vigorous stirring to 220 ml. of concentrated sulfuric acid keeping the temperature at 20-25 C. by external cooling. The solution was allowed to stand a total of 40 hours at room temperature before pouring with gentle agitation onto 660 grams of crushed ice. Neutralization of the resulting solution with ammonium hydroxide precipitated the crude product which was readly purified by a char treatment in hot aqueous methanol. The N ethyl N ,B carbamylethyl-m-toluidine melted at 5759 C.

Example II N,N bis(/8-cyanoethyl)-m-toluidine (30 grams) was slowly added with vigorous stirring to 180 ml. of concenparts and percentages are by weight 3,342,800 Patented Sept. 19, 1967 Example III N,N-bis(fl-cyanoethyl) aniline (30 grams) was slowly added with vigorous stirring to 180 ml. of concentrated sulfuric acid, keeping the temperature at 2025 C. by external cooling. After the initial exothermic reaction subsided, the solution was allowed to stand at room temperature for 64 hours. The reaction mixture was then filtered and the filtrate was poured with stirring onto 640 grams of crushed ice and the N,N-bis(fl-carbamylethyl) aniline was precipitated by neutralization with ammonium hydroxide. The granular white product melted at 152154 C. Recrystallization from ethanol gave a product melting at 154.5155.5 C. The elemental analysis of the product is as follows:

Calculated for C H N O C, 61.4%; N, 17.8%; H 7.2%. Found: C, 61.39%; N, 17.60%; H, 7.18%.

Example IV N,N bis([3-carbamylethyl)-m-chloroaniline was prepared from N,N bis(fl cyanoethyl)-m-chloroaniline in accordance with the procedure in Example II. The product was obtained asolT-white needles melting at 163- 165 C.

Diazotized 2 amino 6 methylsulfonylbenzothiazole was coupled to N ethyl-N-carbamylethyl-m-toluidine according to the following procedure:

Example V 116 grams concentrated sulfuric acid was diluted with 4.2 grams of ice, cooled to 30 C. and 6.8 grams of 2- amino 6 methylsulfonylbenzothiazole was added and stirred until solution was effected. Then 2.14 grams of sodium nitrite was added at 20-25" C. and the solution stirred for 30 minutes. After cooling to 12-18 C., 66 grams of ice was added to further reduce the temperature to 2-6 C. The solution was stirred for an additional hour and then urea was added to destroy excess nitrous acid. The diazo was slowly added at 0-5 C. to a solution of N-ethyl N B carbamylethyl-m-toluidine in dilute hydrochloric acid and stirred for two hours at 05 C. Pouring into water caused the dye to precipitate from solution. Is was separated by filtration and washed with water. It has the following structure.

S C Be It colors cellulose acetate textile materials red shades which have excellent fastness to light and gas, and excellent discharge properties.

Example VI O aOzS Example VII Coupling N,N bis(/3 carbamylethyl) aniline with the diazo of 2 amino 6 methylsulfonylbenzothiazole in accordance with the general procedure described in Example V forms a dye compound. It colors cellulose acetate textile materials red shades having excellent "fastness properties. The dye is also easily dischargeable to pure white shades.

Example VIII The coupling component N,N bis(fi carbamylethyl) m-chloroaniline, was reacted with the diazo of 2 amino- 6 methylsulfonylbenzothiazole in accordance with the procedure in Example V. The dye compound obtained, colors cellulose acetate textile materials red shades.

Example IX Diazotization of 2 amino 6 methylsulfonylbenzothiazole and coupling with N fi-carbamylethyl-m-chloroaniline was carried out in accordance with Example V. The dye compound obtained, colors cellulose acetate textile materials red shades having good discharge and fastness properties.

Example X N B carbamylethyl-o-chloroaniline so obtained was also coupled with diazotized 2 amino 6-methylsulfonylbenzothiazole. The resulting material dyes cellulose acetate textile materials red shades which have excellent fastness to light and gas, and excellent discharge properties.

Example XI Following the general method of Example I, N-phenyl- N-carbamylethyl-aniline was coupled with the diazo of Z-amino 6 methylsulfonylbenzothiazole. The material produced colors cellulose acetate textile materials red shades.

Exmple XII Coupling N,N-bis(,B-carbamylethyl)-m-anisidine with the diazo compound of Z-amino-6-methylsulfonylbenzothiazole forms a dye that colors cellulose acetate textile materials reddish-violet shades. These colors exhibit excellent fastness and dischargeability.

Example XIII When diazotized 2 amino-6-methylsulfonylbenzothiazole is coupled to N-B-carbamylethyl-m-anisidine a dye compound is formed which colors cellulose acetate textile materials reddish-violet shades which have excellent fastness and discharge properties.

Example XIV N-B-carbamylethyl-o-anisidine when coupled with diazotized 2-amino-6-methylsulfonylbenzothiazole gives a dye which colors cellulose acetate textile materials reddish-violet shades which have excellent fastness to light and gas, and excellent discharge properties.

Example XV wherein R represents a member selected from the group consisting of H, lower alkyl, phenyl, and carbamylethyl;

4 R represents carbamylethyl, R and R represent radicals of the class consisting of lower alkyl, methoxy, chlorine, and H.

2. The azo compound having the formula:

I OH;

3. The azo compound having the formula:

C-N=N N(CH2CH2CNI'I2) CHaOzS 4. The azo compound having the formula:

CN=N N(CHzCH2CNHq)1 CH30zS- \S (H) 5. The azo compound having the formula:

C-N=N N(CH2CH2CNH2)2 CH302S I 6. The azo compound having the formula:

C-N=N N CH302S 1 omomoNm 7. The azo compound having the formula:

CN=-N -N\ CHBOZS 1 omorrzoNrr,

8. The azo compound having the formula:

C--N=N N\ E CHMS- CHzCHzCNH;

9. The azo compound having the formula:

C-N=N N(CH;CHCNH)1 CHaOzS- s CHaO 10. The azo compound having the formula:

oN=N N\ (H) CHSOZS CH2CH2CNH3 S OH:

11'. The azo compound having the formula: H

CN=N N f oH'iornoNHi v s 0 CH;

- o CHaOzS- II CH2CH2CNH S OCH 13. The azo compound having the formula:

6 References Cited UNITED STATES PATENTS 2,346,013 4/1944 Dickey 260158 X 2,785,157 3/1957 Straley et a1. 260158 3,084,153 4/1963 Fishwick et a1. 260-158 FOREIGN PATENTS 787,369 12/1957 Great Britain. 894,012 4/1962 Great Britain.

CHARLES B. PARKER, Primary Examiner. D. PAPUGA, Assistant Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,342,800 September 19, 1967 Jack L. Towle et al.

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 4, lines 64 to 68, for the left-hand portion of the formula reading N C\C read cH 0 s S/ cn o s 8/ column 5, lines 2 to 6, for the right-hand portion of the formula reading Signed and sealed this 24th day of September 1968.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. EDWARD J.

BRENNER Attesting Officer Commissioner of Patents 

1. AZO COMPOUNDS OF THE GENERAL FORMULA 